Azo dyestuffs containing aminopyridone coupling component

ABSTRACT

Azo dyestuffs of the formula ##STR1## in which D represents the radical of a diazo component, 
     R denotes alkyl, cycloalkyl, aralkyl or aryl, 
     X represents a nitrile group or an optional substituted carbonamide or carboxylic acid ester group, 
     A represents oxygen 
     Wherein 
     R 1  -r 4  denote hydrogen, alkyl or aralkyl as well as their preparation and use for dyeing of synthetic materials are disclosed. For example, polyolefines, polyvinyl polymers, cellulose 2 1/2 acetate, cellulose triacetate and particularly polyesters are dyed by customary dyeing and printing proceses to give yellow to blue dyeings and prints with good fastness properties especially fastness to light and sublimation.

The present invention relates to azo dyestuffs which are free ofsulphonic acid groups and carboxylic acid groups, of the formula##STR2## in which D represents the radical of a diazo component,

R denotes alkyl, cycloalkyl, aralkyl or aryl,

X represents a nitrile group or an optionally substituted carbonamide orcarboxylic acid ester group,

A represents oxygen

Wherein

R₁ -r₄ denote hydrogen, alkyl or aralkyl and to their preparation anduse for dyeing synthetic fibre materials, especially polyester fibrematerials.

Suitable radicals D are aromatic-carbocyclic radicals, especially thoseof the benzene, diphenyl, naphthalene and anthraquinone series, andaromatic-heterocyclic radicals, preferably those of the thiadiazole,triazole, benztriazole, indole, benzthiazole and oxdiazole series.

Preferred radicals D are radicals of the benzene, thiadiazole andbenzthiazole series. These radicals can possess further non-ionicsubstituents customary in dyestuff chemistry. As examples there may bementioned: halogen atoms, such as chlorine, bromine and fluorine, alkyl,alkoxy, aryl, aryloxy, nitro, cyano, trifluoromethyl, alkylcarbonyl,alkoxycarbonyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl,alkylcarbonylamino, arylcarbonylamino, arylazo, sulphamoyl and carbamoylradicals; alkyl and alkoxy are preferably to be understood as radicalsof this type with 1-4 C atoms and aryl is preferably to be understood asphenyl radicals which are optionally substituted by halogen, C₁ -C₄-alkyl and C₁ -C₄ -alkoxy.

Suitable radicals X, in addition to the nitrile radical, are carbonamideradicals of the formula ##STR3## in which Q₁ and Q₂ independently of oneanother represent hydrogen, alkyl, cycloalkyl, aralkyl or aryl orconjointly with the nitrogen atom form a 5-membered or 6-memberedheterocyclic structure, for example a morpholine, piperidine orpyrrolidine ring, and carboxylic acid ester radicals of the formula

    -COOQ.sub.3

in which

Q₃ represents alkyl or aralkyl.

The alkyl radicals R, R₁ -R₄, Q₁, Q₂ and Q₃ preferably possess 1-6 Catoms and can be substituted, for example by halogen, such as F, Cl orBr, or by cyano, hydroxyl, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonylgroups.

Cycloalkyl radicals R, Q₁ and Q₂ can preferably be cyclohexyl radicalswhich can be substituted by, for example, methyl radicals.

Suitable aryl radicals R, Q₁ and Q₂ are above all phenyl radicals whichare optionally substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen ornitrile; halogen is preferably to be understood as chlorine. The phenyland tolyl radical are preferred.

Suitable aralkyl radicals R, R₁ -R₄, Q₁, Q₂ and Q₃ are preferably benzyland phenylethyl radicals which can be substituted by, for example,chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

The new azo dyestuffs of the formula (I) are obtained, for example, bycombining diazotised amines of the formula

    D-NH.sub.2                                                 (III)

in which

D has the abovementioned meaning with coupling components which in oneof the possible tautomeric forms correspond to the formula ##STR4## inwhich

X, A, R and R₁ have the abovementioned meaning and in the compounds thusobtained, if desired, subsequently alkylating the amino groups in the 4-and 6-position in a manner which is in itself known.

The coupling of the diazotised amines (III) with the compounds (IV) iscarried out in a manner which is in itself known, in a weakly acid,neutral or weakly alkaline, aqueous or organic-aqueous medium, theaddition of an acid-binding agent, such as, for example, sodium acetate,being advisable at times.

As examples of suitable diazo components of the formula (III) there maybe mentioned: aniline, 2-, 3- and 4-N,N-dimethylamino-aniline, 2-, 3-and 4-aminotoluene, 3- and 4-amino-benzotrifluoride, 3- and4-amino-1,2-dimethyl-benzene, 2-, 4- and 5-amino-1,3-dimethylbenzene,4-amino-1,3,5-trimethylbenzene, 2-, 3- and 4-aminoanisole, 2-, 3- and4-aminophenetole, 2-amino-1,4-dimethoxybenzene,2-amino-1,4-diethoxybenzene, 2-, 3- and 4-chloroaniline, 2-, 3- and4-bromoaniline, 2,3-, 2,4-, 2,5- and 3,4-dichloroaniline,2,5-dibromoaniline, 2,4,5-, 2,4,6-, 3,4,5- and 3,4,6-trichloroaniline,3-, 4-, 5-and 6-chloro-2-amino-toluene, 4-chloro-3-amino-toluene,2-chloro-4-amino-toluene, 5-chloro-2-amino-benzotrifluoride, 4,5- and4,6-dichloro-2-amino-toluene, 2,5- and 4,6-dichloro-3-amino-toluene,2,5- and 3,5-dichloro-4-amino-toluene, 4,5,6-trichloro-2-amino-toluene,4-chloro-2-amino-1,3-dimethylbenzene, 6-chloro-3-amino-anisole,2-chloro-4-amino-anisole, 3-chloro-4-aminoanisole, 2-, 3- and4-nitroaniline, 3-nitro-4-amino-toluene,5-nitro-4-amino-1,3-dimethylbenzene, 6-nitro-3-amino-anisole,3-nitro-4-amino-anisole, 5-nitro-2-aminophenetole,2-nitro-4-amino-phenetole, 3-nitro-4-amino-phenetole,5-nitro-2-amino-1,4-dimethoxy-benzene,5-nitro-2-amino-1,4-diethoxy-benzene, 2-chloro-4-nitroaniline,2-bromo-4-nitroaniline, 4-chloro-2-nitroaniline, 4-bromo-2-nitroaniline,2,6-dichloro-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline,2,6-dibromo-4-nitroaniline, 2,4-dinitroaniline,6-chloro-2,4-dinitroaniline, 6-bromo-2,4-dinitroaniline,2,4,6-trinitroaniline, 2-, 3- and 4-amino-benzonitrile,1-amino-2-cyano-5-chlorobenzene, 2-cyano-4-nitroaniline,4-cyano-3-nitroaniline, 2,5-dichloro-4-aminosulphonylaniline,4-methylsulphonylaniline, 1-amino-2,4-dicyanobenzene,1-amino-2,6-dicyano-4-nitrobenzene,1-amino-2-chloro-4-methyl-sulphonylbenzene,2-methylsulphonyl-4-nitroaniline, 4-methylsulphonyl-2-nitroaniline, 2-,3- and 4-amino-benzaldehyde, 2-, 3- and 4-amino-acetophenone,2-amino-5-nitro-acetophenone, 2-, 3- and 4-amino-benzophenone, 2-, 3-and 4-amino-4'-methyl-benzophenone, 2-, 3- and4-amino-4'-methoxy-benzophenone, 4-amino-5-nitro-benzophenone, 2-, 3-and 4-amino-benzoic acid ethyl ester, 2-, 3- and 4-aminobenzoic acidn-butyl ester, 2-, 3- and 4-amino-benzoic acid cyclohexyl ester, 2-, 3-and 4-amino-benzoic acid amide, 2-, 3- and 4-amino-benzoic acidmonomethylamide, 2-, 3- and 4-amino-benzoic acid dimethylamide, 2-, 3-and 4-amino-benzoic acid ethyleneimide, 2-, 3- and 4-amino-benzoic acidisopropylamide, 2-, 3- and 4-amino-benzoic acid diethylamide, 2-, 3- and4-amino-benzoic acid di-n-butylamide, 2-, 3- and 4-aminobenzoic acidmorpholide, 2-, 3- and 4-amino-benzoic acid anilide, 2-, 3- and4-amino-benzoic acid N-methylanilide, 2-, 3- and 4-amino-phenyl aceticacid ester, 2-, 3- and 4-aminophenyl β -methoxy-propionic acid ester,2-, 3- and 4-aminophenyl phenylacetic acid ester, 2-, 3- and4-amino-phenyl phenoxyacetic acid ester, 2-, 3- and 4-amino-phenylbenzoic acid ester, 2-, 3- and 4-amino-phenyl methylsulphonic acidester, 2-, 3- and 4-amino-phenyl ethylsulphonic acid ester, 2-, 3- and4-amino-phenyl β-chloroethylsulphonic acid ester, 2-, 3- and4-amino-phenyl butylsulphonic acid ester, 2-, 3- and 4-amino-phenyln-hexylsulphonic acid ester, 2-, 3- and 4-amino-phenyl phenylsulphonicacid ester, 2-, 3- and 4-aminophenyl (4'-methyl-phenyl)-sulphonic acidester, 2-, 3- and 4-amino-phenyl (4'-methoxy-phenyl)-sulphonic acidester, 2-, 3- and 4-amino-phenyl β -ethoxy-ethylsulphamic acid ester,2-, 3- and 4-amino-benzenesulphonic acid ethyl ester, 2-, 3- and4-amino-benzenesulphonic acid phenyl ester, 2-, 3- and 4-amino-phenyldimethylsulphamic acid ester, 2-, 3- and 4-amino-phenyl ethylsulphamicacid ester, 2-, 3- and 4-aminophenyl diethylsulphamic acid ester, 2-, 3-and 4-amino-phenyl di-n-butylsulphamic acid ester, 2-, 3- and4-amino-phenyl cyclohexylsulphamic acid ester, 2-, 3- and4-amino-benzenesulphonic acid amide, 2-, 3- and 4-amino-benzenesulphonicacid monomethylamide, 2-, 3- and 4-aminobenzenesulphonic aciddimethylamide, 2-, 3- and 4-amino-benzenesulphonic acid ethyleneimide,2-, 3- and 4-amino-benzenesulphonic acid diethylamide, 2-, 3- and4-amino-benzenesulphonic acid di-n-butylamide, 2-, 3- and4-amino-benzenesulphonic acid morpholide, 2-, 3- and4-amino-benzenesulphonic acid cyclohexylamide, 2-, 3- and4-amino-benzenesulphonic acid anilide, 2-, 3- and4-amino-benzenesulphonic acid N-methyl-anilide,1-methyl-2-amino-benzene-4-sulphonic acid amide,1-methoxy-2-amino-benzene-4-sulphonic acid amide,1-methoxy-2-amino-benzene-4-sulphonic acid N-methylanilide,1-chloro-2-amino-benzene-4-sulphonic acid dimethylamide,1-chloro-2-amino-benzene-5-sulphonic acid β-ethoxy-ethylamide,1-chloro-3-amino-benzene-4-sulphonic acid amide,1-chloro-4-amino-benzene-2-sulphonic acid dimethylamide,4-amino-benzene-methylurethane, 2- 3- and 4-amino-acetanilide, 2-, 3-and 4-amino-phenoxyacetanilide, 2-, 3- and 4-amino-N-methyl-acetanilide,4-amino-diphenyl, 4-amino-diphenyl-4'-carboxylic acid ethyl ester,4-amino-4'-acetylamino-diphenyl, 4-amino-2',4'-dinitro-diphenylamine,4-amino-3-nitro-diphenylamine-4'-sulphonic acid amide,1-aminonaphthalene, 1-amino-5-ethoxy-naphthalene,2-chloro-1-aminonaphthalene, 2-amino-naphthalene,2-amino-naphthalene-6-sulphonic acid dimethylamide,5-nitro-2-amino-thiazole, 4-amino-azo-benzene,2',3-dimethyl-4-amino-azo-benzene,2-methyl-4-amino-5-methoxy-azo-benzene, phenyl-azo-4-amino-naphthalene,4-methylsulphonylaniline, 2-aminothiazole, 2-amino-5-nitrothiazole,2-amino-5-thiocyanatothiazole, 2-aminobenzthiazole,2-amino-6-methoxybenzthiazole, 2-amino-6-ethoxybenzthiazole,2-amino-6-chlorobenzthiazole, 2-amino-4,5-dichlorobenzthiazole,2-amino-5,6-dichlorobenzthiazole, 3-amino-5-nitrobenzisothiazole and3-phenyl-5-amino-thiadiazole-(1,2,4).

The coupling components (IV) have not previously been described.

However, these new compounds are obtained easily by reacting pyridiniumsalts of the formula (V) ##STR5## with at least 2 equivalents of anaqueous inorganic base at temperatures of 20° to 150° C, preferably 40°to 100° C, and converting the nitrile group in a manner which is initself known into ester or amide groups.

Suitable inorganic bases are aqueous solutions of NaOH, KOH, Na₂ CO₃, K₂CO₃, NaHCO₃ and others.

The pyridinium salts (V) are in part known from Angew. Chemie 84, 1184(1972) or obtainable according to the process described there.

Examples of suitable coupling components (IV) are:1-methyl-3-cyano-4-methylamino-6-amino-pyridone-2,1-ethyl-3-cyano-4-ethylamino-6-amino-pyridone-2,1-n-propyl-3-cyano-4-n-propylamino-6-amino-pyridone-2,1-i-propyl-3-cyano-4-i-propylamino-6-amino-pyridone-2,1-n-butyl-3-cyano-4-n-butyl-amino-6-amino-pyridone-2,1-i-amyl-3-cyano-4-i-amylamino-6-amino-pyridone-2,1-n-hexyl-3-cyano-4-n-hexylamino-6-aminopyridone-2,1-cyclohexyl-3-cyano-4-cyclohexylamino-6-aminopyridone-2,1-benzyl-3-cyano-4-benzylamino-6-amino-pyridone-2,1-phenethyl-3-cyano-4-β-phenethylamino-6-amino-pyridone-2,1-phenyl-3-cyano-4-anilino-6-amino-pyridone-2,1-p-tolyl-3-cyano-4-p-tolylamino-6-amino-pyridone-2,1-p-ethylphenyl-3-cyano-4-p-ethylphenylamino-6-amino-pyridone-2,1-p-methoxyphenyl-3-cyano-4p-methoxyphenylamino-6-amino-pyridone-2,1-p-chlorophenyl-3-cyano-4-p-chlorophenylamino-6-amino-pyridone-2,1-p-cyanophenyl-3-cyano-4-p-cyanophenylamino-6-amino-pyridone-2,1-β-chloroethyl-3-cyano-4-β-chloroethylamino-6-aminopyridone-2,1-β-hydroxyethyl-3-cyano-4-β-hydroxyethylamino-6-amino-pyridone-2, 1-β-methoxyethyl-3-cyano-4-β-methoxyethyl-amino-6-amino-pyridone-2,1-β-cyanoethyl-3-cyano-4-β-cyanoethylamino-6-amino-pyridone-2, γ-γ-methoxypropyl-3-cyano-4-γ-methoxypropylamino-6-amino-pyridone-2,1-methyl-3-cyano-4-ethylamino-6-amino-pyridone-2,1-ethyl-3-cyano-4-methylamino-6-amino-pyridone-2,1-methyl-3-cyano-4-n-butylamino-6-amino-pyridone-2,1-n-butyl-3-cyano-4-methylamino-6-amino-pyridone-2,1-benzyl-3-cyano-4-methylamino-6-amino-pyridone-2,1-methyl-3-cyano-4-benzylamino-6-amino-pyridone-2,1-methyl-3-cyano-4-anilino-6-amino-pyridone-2,1-methyl-2-imino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-methylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-ethylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-n-propylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-n-butylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-n-hexylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-benzylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-ethyl-2-benzylimino-3-cyano-4-ethylamino-6-amino-1,2-dihydropyridine,1-phenyl-2-benzylimino-3-cyano-4-anilino-6-amino-1,2-dihydropyridine,1-methyl-2-phenylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-p-tolylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-p-chlorophenylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-p-methoxyphenylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-β-phenethylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-β-chloroethylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-β-hydroxyethylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-β-methoxyethylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-β-cyanoethylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-benzylimino-3-cyano-4-ethyl-amino-6-amino-1,2-dihydropyridine,1-ethyl-2-benzylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-ethyl-2-benzylimino-3-cyano-4-butylamino-6-amino-1,2-dihydropyridine,1-ethyl-2-phenylimino-3-cyano-4-ethylamino-6-amino-1,2-dihydropyridine,1-phenyl-2-phenylimino-3-cyano-4-anilino-6-amino-1,2-dihydropyridine,1-methyl-2-β-methoxyethylimino-3-cyano-4-benzylamino-6-amino-1,2-dihydropyridine,1-methyl-3-cyano-4-dimethylamino-6-amino-pyridone-2,1-methyl-3-cyano-4-dimethylamino-6-methylamino-pyridone-2,1-methyl-3-cyano-4,6-bis(dimethylamino)-pyridone-2,1-methyl-3-cyano-4-N-methyl-N-ethylamino-6-diethylamino-pyridone-2,1-methyl-3-cyano-4-N-methyl-N-benzylamino-6-amino-pyridone-2,1-methyl-3-cyano-4-N-methyl-N-benzylamino-6-benzylamino-pyridone-2,1-methyl-2-benzylimino-3-cyano-4-N-methyl-N-benzylamino-6-benzylamino-1,2-dihydropyridine,1-methyl-2-γ-hydroxypropylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-β-hydroxypropylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-γ-methoxypropylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,1-methyl-2-γ-ethoxypropylimino-3-cyano-4-methylamino-6-amino-1,2-dihydropyridine,as well as the corresponding 2-pyridones or 2-imino-1,2-dihydropyridineswhich are substituted in the 3-position by a carbonamide or carboxylicacid ester group.

The new dyestuffs are very suitable for dyeing and printing structuresof synthetic materials such as, for example, polyolefines, polyvinylcompounds, cellulose 21/2-acetate, cellulose triacetate and especiallypolyester materials, for example polyethylene glycol terephthalate. Onthese they give, by the customary dyeing and printing processes, yellowto blue dyeings and prints with good fastness properties, especiallygood fastness to light and sublimation.

The materials mentioned are appropriately dyed from aqueous suspensionin the presence of carriers between about 80° C and 110° C, in theabsence of carriers between about 110° C and 140° C, or by thethermofixing process at about 170° C and 230° C. Printing can be carriedout by steaming the printed goods in the presence of a carrier attemperatures between 80° C and 100° C or in the absence of a carrier atabout 110° C to 140° C or treating them by the thermofixing process atabout 170° C and 230° C.

In the examples which follow, parts denote parts by weight andpercentages denote percentages by weight.

EXAMPLE 1

23.3 parts of 1-methyl-2-chloro-3-cyano-4-methylamino-6-amino-pyridiniumchloride (prepared according to the instructions of A. L. Cossey; Angew,Chemie 84 (1972) 1185) are dissolved in approx. 500 parts by volume ofwater at 40°-50° C and somewhat more than 21.5 parts of sodium carbonate(as a 20% strength aqueous solution) are added over the course of 1 to 2hours at 60°-80° C, the pH value of the reaction solution being keptconstantly at 7.5-8.5. The separating-out of the pyridone whichcrystallises out after a short time is completed, after the end of thereaction, by cooling the reaction mixture to room temperature, and thereaction product which precipitates is filtered off, washed with waterand dried. The compound of the formula ##STR6## which melts at 308-310°C is obtained in 90-95% yield.

EXAMPLE 2

26.1 parts of the1-ethyl-2-chloro-3-cyano-4-ethylamino-6-amino-pyridinium chlorideprepared by the method of A. L. Cossey et al (Angew. Chemie 84 (1972)1185) from N-ethylcyanoacetamide and phosphorus oxychloride inchloroform are dissolved in approx. 500 parts by volume of water at40°-50° C and approximately 22 to 25 parts of sodium carbonate are addedover the course of one to two hours at 60°-80° C, whilst keeping the pHvalue of the reaction solution constantly at 7.5-8.5. The separating-outof the pyridone which crystallises out after a short time is completed,after the reaction has ended, by cooling the reaction mixture to roomtemperature and the product which precipitates is filtered off, washedwith water and dried. After recrystallisation from ethanol, the compoundof the formula ##STR7## which melts at 270°-272° is obtained in 85-90%yield.

EXAMPLE 3

17.8 parts of the pyridone described in Example 1 are introduced into100 parts of 90% strength sulphuric acid whilst stirring. The mixture isthen heated to 90°-85° C for two hours, cooled and poured into icewater. The pH value of the solution is then adjusted to 7-8 by addingdilute sodium hydroxide solution whilst cooling and the precipitate isthereafter filtered off, thoroughly washed with water and dried.Approximately 17 parts of a colourless compound of the formula ##STR8##melting at 253°-256° C are obtained.

EXAMPLE 4

12.75 parts of p-chloroaniline are diazotised in the usual manner inaqueous solution, containing hydrochloric acid, by means of 6.9 parts ofsodium nitrite (as a 30% strength aqueous solution) at 0°-5° C. Theclarified diazonium salt solution is added to a solution of 19.6 partsof 1-methyl-3-cyano-4-methylamino-6-amino-pyridone-2 in approx. 200parts by volume of dimethylformamide and 50 parts by volume of water. Tocomplete the coupling reaction, the pH value of the coupling solution issubsequently raised to about 3 to 4 by adding aqueous sodium acetatesolution and the dyestuff which has precipitated, of the formula##STR9## is then filtered off, washed with water and dried.Approximately 29 parts of a yellow powder are obtained.

Dyeing example

1 part of the dyestuff obtained in the preceding example and finelydispersed according to customary processes is introduced into 2,000parts of water. The pH value is adjusted to 5-6 with acetic acid and 4parts of ammonium sulphate and 2 parts of a commercially availabledispersing agent based on a naphthalenesulphonic acid/formaldehydecondensate are added. 100 parts of a polyester fabric based onpolyethylene glycol terephthalate are introduced into the dyeing liquorthus obtained and dyed for 11/2 hours at 120°-130° C. After subsequentrinsing, reductive after-treatment with an 0.2% strength alkaline sodiumdithionite solution for 15 minutes at 60° C, rinsing and drying, agreenish-tinged yellow dyeing having good fastness properties isobtained.

EXAMPLE 5

16.2 parts of 2,5-dichloroaniline are diazotised as described in Example6 and combined with a solution of 21 parts of1-methyl-3-carbonamido-4-methylamino-6-amino-pyridone-2 in approx. 200parts by volume of dimethylformamide and 50 parts by volume of water.After addition of aqueous sodium acetate solution, the dyestuff whichprecipitates, of the formula ##STR10## is filtered off, washed withwater and dried. Approx. 33 parts of yellow dyestuff powder, which dyespolyester materials in clear yellow shades having good fastnessproperties, are obtained.

The table which follows indicates further dyestuffs according to thepresent invention and the colour shades of dyeings or prints which areobtainable therewith on polyester materials and which also possess goodfastness properties.

                                      Table                                       __________________________________________________________________________     ##STR11##                                                                                                                      Colour shade on             No. D                  A       R       R.sub.1 to R.sub.4                                                                       polyester                   __________________________________________________________________________    1.  Phenyl             O       CH.sub.3                                                                              R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = CH.sub.3                     2.  2-Nitrophenyl      O       CH.sub.3                                                                              "          yellow                      3.  3-Nitrophenyl      O       CH.sub.3                                                                              "          yellow                      4.  4-Nitrophenyl      O       CH.sub.3                                                                              "          yellow                      5.  2-Chlorophenyl     O       CH.sub.3                                                                              "          yellow                      6.  3-Chlorophenyl     O       CH.sub.3                                                                              "          yellow                      7.  2,4-Dichlorophenyl O       CH.sub.3                                                                              "          yellow                      8.  2,5-Dichlorophenyl O       CH.sub.3                                                                              "          yellow                      9.  3,5-Dichlorophenyl O       CH.sub.3                                                                              "          yellow                      10. 3,4,6-Trichlorophenyl                                                                            O       CH.sub.3                                                                              "          yellow                      11. 2-Methylphenyl     O       CH.sub.3                                                                              "          yellow                      12. 3-Methylphenyl     O       CH.sub.3                                                                              "          yellow                      13. 4-Methylphenyl     O       CH.sub.3                                                                              "          yellow                      14. 3-Trifluoromethylphenyl                                                                          O       CH.sub.3                                                                              "          yellow                      15. 4-Trifluoromethylphenyl                                                                          O       CH.sub.3                                                                              "          yellow                      16. 2-Methoxyphenyl    O       CH.sub.3                                                                              "          yellow                      17. 3-Methoxyphenyl    O       CH.sub.3                                                                              "          yellow                      18. 4-Methoxy-phenyl   O       CH.sub.3                                                                              "          yellow                      19. 4-Ethoxyphenyl     O       CH.sub.3                                                                              "          yellow                      20. 4-Bromophenyl      O       CH.sub.3                                                                              "          yellow                      21. 2-Chloro-4-methylphenyl                                                                          O       CH.sub.3                                                                              "          yellow                      22. 3-Chloro-4-methylphenyl                                                                          O       CH.sub.3                                                                              "          yellow                      23. 2-Methyl-4-chlorophenyl                                                                          O       CH.sub.3                                                                              "          yellow                      24. 2-Trifluoromethyl-4-chloro-                                                                      O       CH.sub.3                                                                              "          yellow                          phenyl                                                                    25. 2-Methyl-4,5-dichlorophenyl                                                                      O       CH.sub.3                                                                              "          yellow                      26. 2-Chloro-4-methoxyphenyl                                                                         O       CH.sub.3                                                                              "          yellow                      27. 2-Nitro-4-methylphenyl                                                                           O       CH.sub.3                                                                              "          yellow                      28. 2-Nitro-4-methoxyphenyl                                                                          O       CH.sub.3                                                                              "          yellow                      29. 2-Chloro-4-nitrophenyl                                                                           O       CH.sub.3                                                                              "          yellow                      30. 2-Bromo-4-nitrophenyl                                                                            O       CH.sub.3                                                                              "          yellow                      31. 2-Nitro-4-chlorophenyl                                                                           O       CH.sub.3                                                                              "          yellow                      32. 2,6-Dichloro-4-nitrophenyl                                                                       O       CH.sub.3                                                                              "          yellow                      33. 2,4-Dinitrophenyl  O       CH.sub.3                                                                              "          red                         34. 2,4-Dinitro-6-bromophenyl                                                                        O       CH.sub.3                                                                              "          red                         35. 2,4-Dinitro-6-cyanophenyl                                                                        O       CH.sub.3                                                                              "          red                         36. 2-Cyanophenyl      O       CH.sub.3                                                                              "          yellow                      37. 3-Cyanophenyl      O       CH.sub.3                                                                              "          yellow                      38. 4-Cyanophenyl      O       CH.sub.3                                                                              "          yellow                      39. 2-Cyano-5-chlorophenyl                                                                           O       CH.sub.3                                                                              "          yellow                      40. 2-Cyano-4-nitrophenyl                                                                            O       CH.sub.3                                                                              "          orange                      41. 2,4-Dicyanophenyl  O       CH.sub.3                                                                              "          orange                      42. 3,4-Dicyanophenyl  O       CH.sub.3                                                                              "          yellow                      43. 4-Methylsulphonylphenyl                                                                          O       CH.sub.3                                                                              "          yellow                      44. 2-Nitro-4-methylsulphonylphenyl                                                                  O       CH.sub.3                                                                              "          orange                      45. 3-Acetylphenyl     O       CH.sub.3                                                                              "          yellow                      46. 4-Acetylphenyl     O       CH.sub.3                                                                              "          yellow                      47  4-Benzoylphenyl    O       CH.sub.3                                                                              "          yellow                      48. 2-Carboethoxyphenyl                                                                              O       CH.sub.3                                                                              "          yellow                      49. 3-Carboethoxyphenyl                                                                              O       CH.sub.3                                                                              "          yellow                      50. 4-Carbomethoxyphenyl                                                                             O       CH.sub.3                                                                              "          yellow                      51. 4-Carboethoxyphenyl                                                                              O       CH.sub.3                                                                              "          yellow                      52. 4-Carbo-β-ethoxyethoxyphenyl                                                                O       CH.sub.3                                                                              "          yellow                      53. 3-Acetaminophenyl  O       CH.sub.3                                                                              "          yellow                      54. 4-Acetaminophenyl  O       CH.sub.3                                                                              "          yellow                      55. 4-Carbonamidophenyl                                                                              O       CH.sub.3                                                                              "          yellow                      56. 4-N-Methylcarbonamidophenyl                                                                      O       CH.sub.3                                                                              "          yellow                      57. 4-N,N-Diethylcarbonamidophenyl                                                                   O       CH.sub.3                                                                              "          yellow                      58. 3-Sulphonamidophenyl                                                                             O       CH.sub.3                                                                              "          yellow                      59. 4-Sulphonamidophenyl                                                                             O       CH.sub.3                                                                              "          yellow                      60. 3-Sulphamidoxyphenyl                                                                             O       CH.sub.3                                                                              "          yellow                      61. 4-Sulphamidoxyphenyl                                                                             O       CH.sub.3                                                                              "          yellow                      62. 3-N,N-Diethylsulphamidoxyphenyl                                                                  O       CH.sub.3                                                                              "          yellow                      63. 4-Phenylsulphonyloxyphenyl                                                                       O       CH.sub.3                                                                              "          yellow                      64. 3-p-Toluenesulphonyloxyphenyl                                                                    O       CH.sub.3                                                                              "          yellow                      65. 2-Carbomethoxy-4-nitrophenyl                                                                     O       CH.sub.3                                                                              "          reddish-                                                                      tinged orange               66. 2-Methyl-5-sulphonamidophenyl                                                                    O       CH.sub.3                                                                              "          yellow                      67. 4-β-Methoxyethoxycarbonyloxy-                                                               O       CH.sub.3                                                                              "          yellow                          phenyl                                                                         ##STR12##         O       CH.sub.3                                                                              "          yellow                      69. 4-Phenylphenyl     O       CH.sub.3                                                                              "          yellow                      70. 4-Cyclohexylphenyl O       CH.sub.3                                                                              "          yellow                      71. 4-tert. Butylphenyl                                                                              O       CH.sub.3                                                                              "          yellow                      72. 2-Nitro-4-cyclohexylphenyl                                                                       O       CH.sub.3                                                                              "          yellow                      73. 2-Nitro-4-tert.-butylphenyl                                                                      O       CH.sub.3                                                                              "          yellow                      74. 4-Phenylaminophenyl                                                                              O       CH.sub.3                                                                              "          yellow                      75. 4-(2',4'-Dinitrophenyl)-                                                                         O       CH.sub.3                                                                              "          orange                          aminophenyl                                                               76. Naphthyl-1         O       CH.sub.3                                                                              "          yellow                      77. Naphthyl-2         O       CH.sub.3                                                                              "          yellow                      78. 2-Chloronaphthyl-1 O       CH.sub.3                                                                              "          yellow                      79. 4-Phenylazophenyl  O       CH.sub.3                                                                              "          orange                      80. 4-Phenylazonaphthyl-1                                                                            O       CH.sub.3                                                                              "          orange                      81. 5-Nitro-thiazolyl-2                                                                              O       CH.sub.3                                                                              "          red                         82. 6-Chloro-benzthiazolyl-2                                                                         O       CH.sub.3                                                                              "          red                         83. 6-Methoxy-benzthiazolyl-2                                                                        O       CH.sub.3                                                                              "          red                         84. 6-Nitro-benzthiazolyl-2                                                                          O       CH.sub.3                                                                              "          red                         85. 6-Methylsulphonyl-benzthiazolyl-2                                                                O       CH.sub.3                                                                              "          red                         86. 4-Chlorophenyl     O       C.sub.2 H.sub.5                                                                       R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = C.sub.2 H.sub.5              87. 2,5-Dichlorophenyl O       C.sub.2 H.sub.5                                                                       "          yellow                      88. 4-Methylphenyl     O       C.sub.2 H.sub.5                                                                       "          yellow                      89. 3-Trifluoromethylphenyl                                                                          O       C.sub.2 H.sub.5                                                                       "          yellow                      90. 4-Methoxyphenyl    O       C.sub.2 H.sub.5                                                                       "          yellow                      91. 2-Chloro-4-nitrophenyl                                                                           O       C.sub.2 H.sub.5                                                                       "          orange                      92. 2-Cyano-4-nitrophenyl                                                                            O       C.sub.2 H.sub.5                                                                       "          red                         93. 4-Methylsulphonylphenyl                                                                          O       C.sub.2 H.sub.5                                                                       "          yellow                      94. 4-Carboethoxyphenyl                                                                              O       C.sub.2 H.sub.5                                                                       "          yellow                      95. 4-Acetaminophenyl  O       C.sub.2 H.sub.5                                                                       "          yellow                      96. 3-Sulphonamidophenyl                                                                             O       C.sub.2 H.sub.5                                                                       "          yellow                      97. 4-Phenylazophenyl  O       C.sub.2 H.sub.5                                                                       "          orange                      98. 4-Chlorophenyl     O       n-C.sub.3 H.sub.7                                                                     R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = n-C.sub.3 H.sub.7            99. 2,5-Dichlorophenyl O       "       "          yellow                      100.                                                                              3,5-Dichlorophenyl O       "       "          yellow                      101.                                                                              4-Carbomethoxyphenyl                                                                             O       "       "          yellow                      102.                                                                              4-Phenylazophenyl  O       "       "          orange                      103.                                                                              2,5-Dichlorophenyl O       i-C.sub. 3 H.sub.7                                                                    R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = i-C.sub. 3 H.sub.7           104.                                                                              4-Phenylazophenyl  O       "       "          orange                      105.                                                                              2,5-Dichlorophenyl O       n-C.sub. 4 H.sub.9                                                                    R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = n-C.sub. 4 H.sub.9           106.                                                                              4-Cyanophenyl      O       "       "          yellow                      107.                                                                              2-Cyano-5-chlorophenyl                                                                           O       "       "          yellow                      108.                                                                              4-Phenylazophenyl  O       "       "          orange                      109.                                                                              2,5-Dichlorophenyl O                                                                                      ##STR13##                                                                            R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                              ##STR14##                             110.                                                                              2-Cyano-4-nitrophenyl                                                                            O       "       "          red                         111.                                                                              4-Phenylazophenyl  O       "       "          orange                      112.                                                                              4-Chlorophenyl     O       CH.sub.2C.sub.6 H.sub.5                                                               R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = CHC.sub.6 H.sub.5            113.                                                                              2,5-Dichlorophenyl O       "       "          yellow                      114.                                                                              2-Cyano-4-nitrophenyl                                                                            O       "       "          red                         115.                                                                              4-Phenylazophenyl  O       "       "          orange                      116.                                                                                "                O       (CH.sub.2).sub.2C.sub.6 H.sub.5                                                       R.sub.1, R.sub.3, R.sub.4 =                                                              orange                                                             R.sub.2 = (CH.sub.2).sub.2C.sub.6                                             H.sub.5                                117.                                                                                "                O                                                                                      ##STR15##                                                                            R.sub.1, R.sub.3, R.sub.4 =                                                              orange                                                              ##STR16##                             118.                                                                              2,5-Dichlorophenyl O                                                                                      ##STR17##                                                                            R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                              ##STR18##                             119.                                                                                "                O       (CH.sub.2).sub.2CN                                                                    R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = (CH.sub.2).sub.2CN           120.                                                                              2,5-Dichlorophenyl O       (CH.sub.2).sub.2OCH.sub.3                                                             R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = (CH.sub.2).sub.2OCH.sub.3                                           1                                      121.                                                                                "                O       CH.sub.3                                                                              R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = C.sub.2 H.sub.5              122.                                                                              4-Phenylazophenyl  O       CH.sub.3                                                                              "          orange                      123.                                                                              4-Chlorophenyl     O       C.sub.2 H.sub.5                                                                       R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = CH.sub.3                     124.                                                                              2,5-Dichlorophenyl O       C.sub.2 H.sub.5                                                                       "          yellow                      125.                                                                              4-Phenylazophenyl  O       C.sub.2 H.sub.5                                                                       "          orange                      126.                                                                              4-Chlorophenyl     O       CH.sub.2C.sub.6 H.sub.5                                                               R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = CH.sub.3                     127.                                                                              2,5-Dichlorophenyl O       CH.sub.3                                                                              R.sub.1, R.sub.3, R.sub.4 =                                                              yellow                                                             R.sub.2 = CH.sub.2C.sub.6 H.sub.5      128.                                                                              2,5-Dichlorophenyl O       CH.sub.3                                                                              R.sub.1, R.sub.3, R.sub.4  =                                                             yellow                                                             R.sub.2 = C.sub.6 H.sub.5              129.                                                                              2,5-Dichlorophenyl O       CH.sub.3                                                                              R.sub.1, R.sub.2                                                                         yellowub.3                                                         R.sub.3, R.sub.4 = H                   130.                                                                              4-Phenylazolphenyl O       CH.sub.3                                                                              "          orange                      131.                                                                              2,5-Dichlorophenyl O       CH.sub.3                                                                              R.sub.1, R.sub.2, R.sub.3 =                                                   CH.sub.3   yellow                                                             R.sub.4 = H                            213.                                                                              4-Phenylazophenyl  O       CH.sub.3                                                                              "          orange                      214.                                                                              2,5-Dichlorophenyl O       CH.sub.3                                                                              R.sub.1, R.sub.2, R.sub.3, R.sub.4                                            = CH.sub.3 yellow                      216.                                                                              4-Phenylazophenyl  O       CH.sub.3                                                                              "          orange                      217.                                                                                "                NCH.sub.2C.sub.6 H.sub.5                                                              CH.sub.3                                                                              "          orange                      132.                                                                                "                O       CH.sub.3                                                                              R.sub.1 = CH.sub.3                                                                       orange                                                             R.sub.2, R.sub.3, R.sub.4 =                                                   C.sub.2 H.sub.5                        133.                                                                                "                O       CH.sub.3                                                                              R.sub.1, R.sub.3 = CH.sub.2C.sub.6                                            H.sub.5    orange                                                             R.sub.2 =  CH.sub.3, R.sub.4 =         __________________________________________________________________________                                           H                                  

If instead of the 3-cyanopyridine derivatives corresponding pyridones or1,2-dihydropyridinimines substituted in the 3-position by carbonamide orcarboxylic acid ester groups are used as coupling components,corresponding diazo components give dyestuffs which dye polyestermaterials in similar colour shades and with similar fastness properties.

We claim:
 1. Azo dyestuff of the formula ##STR19## in which D is theradical of a diazo component;R is C₁ -C₆ -alkyl; C₁ -C₆ -alkylsubstituted by halogen, cyano, hydroxyl, C₁ -C₄ -alkoxy or C₂ -C₅-alkoxycarbonyl; cyclohexyl; cyclohexyl substituted by methyl; phenyl;phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano;benzyl; phenethyl; or benzyl or phenethyl substituted by chlorine, C₁-C₄ -alkyl or C₁ -C₄ -alkoxy; X is cyano R₁ -r₄ are hydrogen; C₁ -C₆-alkyl; C₁ -C₆ -alkyl substituted by halogen, cyano, hydroxyl, C₁ -C₄-alkoxy or C₂ -C₅ -alkoxycarbonyl; benzyl; phenethyl; or benzyl orphenethyl substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy. 2.Azo dyestuff of claim 1 in which D is ##STR20## Y is a halogen; nitro;CN; CF₃ ; C₂ -C₅ -alkyl-carbonylamino; C₁ -C₄ -alkylsulphonyl; C₂ -C₅-alkoxycarbonyl; phenyl; ##STR21## or ##STR22## V₁ and V₂ independentlyof one another are hydrogen or C₁ -C₄ -alkyl;Z is hydrogen, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, CN or halogen; and n is the number 1 or
 2. 3.Azo dyestuff of claim 1 in which D is phenyl; or phenyl substituted byhalogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl, phenyl substituted byhalogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, phenyloxy, phenyloxysubstituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, nitro, cyano,trifluoromethyl, (C₁ -C₄ -alkyl)-carbonyl, (C₁ -C₄ -alkoxy)-carbonyl,phenylcarbonyl, phenylcarbonyl substituted by halogen, C₁ -C₄ -alkyl orC₁ -C₄ -alkoxy, C₁ -C₄ -alkyl sulfonyl, phenylsulfonyl, phenylsulfonylsubstituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, (C₁ -C₄-alkyl)-carbonylamino, phenylcarbonylamino, phenylcarbonylaminosubstituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, phenylazo,phenylazo substituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, orsulfamoyl or carbamoyl.
 4. Azo dyestuff of the formula ##STR23## inwhich R' and R₁ ' are C₁ -C₆ -alkyl substituted by OH, CN, halogen C₁-C₄ -alkoxy or C₂ -C₅ -alkylcarbonyl;X' is CN Y is halogen; nitro; CN;CF₃ ; C₂ -C₅ -alkylcarbonyl-amino; C₁ -C₄ -alkylsulphonyl; C₂ -C₅-alkoxycarbonyl; phenyl; ##STR24## V₁ and V₂ independently of oneanother are hydrogen or C₁ -C₄ -alkyl; Z is hydrogen, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, CN or halogen; and n is the number 1 or 2.